Treatment of wool with acid aminotriazine resin colloids



Patented Sept. 2, 1952 TREATMENT OF WOOL WITH ACID AMINO- TRIAZINE RESIN COLLOIDS Linton Avery Fluck, Pluckemin, and John Edward Lynn,

Old Greenwich, Conn.,

assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application November 14,1949, Serial No. 127,277

This invention relates to the treatment of textilesand more particularly to the treatment of wool and wool-containing fabrics particularly to reduce their felting, fulling and shrinking tendencies.

Wool and wool-containing fabrics such as loose wool "itself, yarns, threads, woven, felted or knitted cloth have a very undesirable tendency to 'felt and shrink when subjected to ordinary washing operations. The tendency of these wool materials to felt and shrink is due generally to a curling and intertwining of the wool fibers as the fabrics are wetted and subjected to the mechanical movements of the washing process. As a result the fabric becomes more closely compacted, thicker, and has a considerably'reduced area.

A number of different methods have been proposed for. the treatment of wool and woolen fabrics to prevent felting and shrinking but all of these have not been completely satisfactory. Some treatments damage the fiber and reduce its wearing qualities, others impart an undesirable hand to the fabric, and some treatments are not permanently effective and may even cause an ultimate increase in shrinkage. Still other shrink-proofing methods are difficult to applywith uniformity and create hazards to the workmen involved in their applications.

One successful method for the treatment of wool to prevent its felting and shrinking is described in the J ohnstone and Van Loo U. S. Reissue Patent No. 22,566. According to the process therein described wool-containing fabrics are treated with alkylated methylol melamine solutions and the alkylated methylol melamine is then cured in the fabric to a water-insoluble condition. However, high temperatures of at leastabout 200 F. and preferably higher are necessary to cure the resin in the fabric.

We have now found that wool and wool-con taining fabrics such as unwoven wool, yarns, worsteds, flannels, felts including hat makers felts, blankets, shirting, knit goods and others, either of all wool, or of part wool and part silk, viscose rayon, acetate rayon, cotton, etc. may be rendered substantially resistant to felting, fulling and shrinking by the application thereto'of a coloidal aqueous solution of a polymerized I cationic aminotriazine-aldehyde condensa tion product containing an acid. It is an advantage of this new process that the high curing temperatures of the -Johnstone and Van Loo process referred to above are not required for rendering theresiri water-i mune.

1 It is an object of the-present invention to 're- 11 Claims. (Cl. 117-141) of wool and wool-containing fabrics. It is another object of the present invention wearing qualities.

It is still another object of the presentinven tion to reduce the felting, fulling and shrinking tendencies of wool and wool-containing fabrics without substantially reducing the tensile strength of the wool. I

A further object of the present inventionis to provide a safe, convenient and effective method for reducing the felting, fulling and shrinking tendencies of wool and wool-containing fabrics.

A still further object of this invention is to improve the wearing characteristics of woolen. goods such. as durability and resistance"to abrasion.

The above and other objects are attainedby impregnating wool or a wool-containing fabric with a colloidal aqueous solution of a polymer-I ized cationic aminotriazine-aldehyde condensation product containing an acid and dryingthe impregnated fabric to convert the aminotriazinealdehyde condensation product deposited in the fabric to a substantially water-insoluble condition.

The invention will be described in greater'detail in conjunction with the following specific examples in which proportions are given in parts by weight unless otherwise indicated. The.examples are merely illustrative and it is not'in tended that the scope of the invention be'limited to the'details therein set forth.

EXAMPLE 1 wool O. D. shirting is treated with a cationic acetic acid colloid of polymerized methylated trimethylol melamine (resin A) by twice immersing the shirting in an 8% resin solids solution and thereafter passing it through suitable rolls, as in a padder, at 3.5 tons pressure so that the wooli-hasa 1 00% wet pick-up The shirting is dried to'size at 225 F. for six-minutes;. and a portion thereof then dolly washed for fiver duce the felting, fulling and shrinking tendencies 2 minutes in a 0.2% solution of N-octadecyl disodium sulfosuccinamate, rinsed for five minutes and then treated for five minutes with a 1% solution of a softening 'agentwhich is the reaction product of from 5.5-6.5 mols of ethylene oxide with 1 mol of a mixture of the octadecylamine salt of N-octadecylcarbamic acid and the octadecylguanidine salt of N-octadecylcarbamic acid as described in U. S. Patent No. 2,427,242. After hydroextraction and drying relaxed at 225 F. the tensile strength of the fabric, measured on a Suter tensile tester by the grab method using a 3 inch length, is found to be 60 .pounds in. the.

direction of the warp and 50 pounds in the direction of the filling. Untreated shirting, after a. five minute light wash and drying, has a tensile strength of 56 pounds in the direction of the warp and 49 pounds in the direction of the filling.

Another portion of the shirting treated as described above:withz resin- A' is 1 neutralized at 160 F. with from;5-=l0% *sodiumxcarbonate.ysolution andhthe-soeneutralized shirting and. some .un-

treated shir'ting are :given five wool washes as fol-.

lows::45 minutes in a reversing. wheel washer-at 100E110: in asolutionwof enough neutral soap to ive't azagood running: suds, vi.. e., from about 0.-1%.-'0.'25%' soap, and three .rinses of ,5 minutes each with' water at 100 110 F. After the last rinse the shirting is centrifuged, dried loose in azforced'circulation oven at 250"1. and then dampened-"and"pressed'dry on an electric flat bedfpressi. The warp shrinkage of the treated material. is :45 while that of the .untreated ma-. terial is 20.5%; the filling shrinkage is 18% for theiuntreateiandj 2 for the .treated.

EXAMPLE ,2

The procedure reduces-the .warp shrinkage of the.

materialfrom 46% to 2.5 andthe filling shrinkagezfron'r29 %:to 1.5%.

EXAlWPLE3 100% woolblanket fabric-is twice immersed in an 8% solids solution of resin A followed by passing through the rolls of a padder under 2 tons pressure and'drying for 9: minutes at 225 F., all in accordance with. the general procedure of Example :1; The fabric is givena light dolly; wash ford minutes; it is then hydroextracted and dried relaxedat 225 F;

The tensile strength of the treated material is 68 pounds in the direction of the warp and 73 pounds in the direction of theifilli-ng; corresponding figures for untreated material are 72 and 76. The warp shrinkage for the treated material is 3.5% while that for untreated material :is 16.5%. The

filling shrinkage drops from for untreated material to 5% for the treated.

EXAMPLEA 8% ounce all-wool block plaid is treated generally'according to the procedure'of Example .1 by twice immersing the wool in an 8% solids solution of resin A and passing through the rolls of a padder under 4 tons pressure. After drying for 6 minutes at 225 F., the fabric is subjected to alight dolly wash for 6 minutes and it is then hydroextracted and driedrelaxed at 225 F.

The warp tensile strength for the treated material is 25 pounds whereas that for untreated material is 23 pounds. The filling tensile strength is 19 pounds for the treated material and 20 pounds for untreated. Warp shrinkage of 20% for untreated material drops to 4.5% for treated, and filling shrinkage of 27% for untreated drops to 4.5% for the treated.

EXAIWPLE 5 the fabric is dolly, washed for 5 minutes in, a. 0.2 solution of N-octadecyl; disodium sulfosuccinae mate, extracted for 5'minutes and dried relaxed at 225 F.

The warp tensile strength is 25 pounds-for both treated anduntreated material and the filling tensile strength is 18'pounds for each. Un-

treated fabric has a warp shrinkage of 23%and filling shrinkage.of,21%; the treated fabric has corresponding; shrinkages; of 3% and 4.5%respectively.

EXAMPLE 6 The procedure ofExamplel is followed exactly on. wool plaid. except that afterthetwo dips.

and two nips the wool is dried to size for?) min: utes instead. of .6.

The warp andfilling tensilestrengths for untreatedmaterial are..25. pounds and 19 pounds, respectively.

and a filling shrinkage of 26%; the treated material has dropped ,to,2.5% warp. shrinkageandj 10 filling shrinkage.

EXAMPLE 7 The procedureof Examplelisgenerally followed and a Buffalo plaid of 100% wool, partly reworked, is twice immersed in a 9% solids solut tion of resin A followed by passing through the rolls of a padderat 1 ton pressure, and thendried to size for 9 minutes at 250 F. The treated plaid is dolly washed for 5 minutes in a solution of N-octadecyl disodium sulfosuccinamate, rinsed for5 minutes with a 1%. solution of a softening agent which is the reaction product of from 5.5- 6.5 mols of ethylene oxide with 1 mol of a mixture of the octadecylamine salt of N-octadecylcarbamic acid and the-octadecylguanidine salt of N-octadecylcarbamic acid as described in U. S. Patent No. 2,427,242. The material is extracted and dried relaxed at 225 F.

Untreated material has a warp tensile strength of 52 pounds and a filling tensile strength of 31 pounds. Corresponding figures for the treated materials-are 44 pounds and 22 pounds, respectively. Warp shrinkage of 25% for untreated material is reduced to 5% for the treated and a filling shrinkage of 23% for untreated, material drops to 3% for the treated.

EXAIVIPLE 8 Again the general procedure of Example .1. is followed and'Buffalo plaid woolen shirting fabric Corresponding figures. for the. treated material are 24 pounds and 19 pounds. Untreated materialhas awarpshrinkage of 32% squeezed at a pressureof 4.5 tons and dried for 9 minutes at 225 F. The treated fabric is dolly washed for minutes in a 0.1% aqueous solution dry'l'weightbr fabric,. the li uor ick-a eriod c be governed accordingly.

After the wool has been impregnated with the alkylated methylol melamine resin colloid, it is ofthedioctyl ester of sodium sulfosuccinic acid, 5 dried at temperatures of from about 65-400 F., rinsed. for 5 minutes, treated for 5 minutes with or preferably from about 180-300 F., whereby the softening agent, vhydroextracted and dried the resin is deposited in the wool in a s'ubstanrelaxed.' v I p} tially water-insoluble condition. Thewarp tensilestrengthof untreated vma- Aminotriazines containing two or three reterialfisll pounds and of the treated material, active amino groups such as melamine, N-guanyl- 36 poundsf'." The filling tensile strengths are 4'7 melamine, ammeline, formoguanamine, acetopounds and 40 pounds, respectively. W a'rp guanamine, propioguanamine, phenylguanamine, shrinkage for untreated material.is25%.and for and, N-a1kyl-, aryland aralkyl-substituted' the'ltreated, 5%.. Filling shrinkage for untreated derivatives thereof such as N methylmelaminq material is 19% and there is no filling shrinkage N phenylmelamine, "N-benzylmelamine, etcfol-the trejated material. f ;which contain a hydrogenatomattached to each results of the foregoing examplesare set nitrogen atom as disclosed in U. =S Patent No. forth in tabularjform for convenience: i 2,197,357 may be reacted with aldehydes toform' Tensile Strength in Lbs. I F "Shrinkage, Percent ,liabric Untreated f g l l efitga l i Untreated Fagfigif figpgf I I u I m viz sssshz. And-5 I a mm.) v Wool Washes 3' wor grm Warp r111 Warp Fill Warp 1 F111 100% woo1 'o. D. 5 49 to 5o 20.5 18 4.5 2

Skirting. 6H9 Wool/Rayon 35 22 31 V12 45 29 2.5 1.5 'F'an'ciesi.

100%Woo1 Blanket-.. 72 7s 68 vs 16.5 25 9.5 5 8% -oz. 100% Wool 23 '25 19; 20 27 4.5 4.5

IBlock Plaid. I 1o0%-Woo1; i '18 25 1s 21 a 4.5 100% woo11 1aid 27 19 24 19 -a2 26 2.5 1 l'00% Wool (partly re- 52 31 g 44 22 25 23 5 3 A worked) Buffalo 7 -Plaid. 2.--- 'Bjifialo Plaidwoolen 3 41 47 36 90 25 19 5 o :sm m 1 'Preparation' of resin A the condensation products which are used for r 1 preparing the cationic colloidal resin'solutions ni fi e fipifi ii o o fifi o iv fi ifi used in the present process; Methylol melamines' ample- 2 of Briti sh Patent No. 566 347 (0.32-mol) obtained by condensing mPlamme with, W 636 parts of water at L90, v p amounts of formaldehyde, 1 e., in molar ratios'of 63 8 parts of glacial acetic acid (ll fuels) 9. '45 about 1:1 to 1:20 but preferably generally of 9 h V 1 1 about 1:2 to 1:6, and their water-disper'sible Th'methylated t f l hy o melamine is com alkylated derivatives obtained by reacting the pletely dissolved by thorough stirring in the methylol melamines with lower aliphatic'alcohols water at 80f- 90 F. The acid is then slowly added such as methanol and ethanol are preferred. with stirring and the mixture is al ow d 1' 0 a Aldehydes other than the formaldehyde of the for {about 12-16 hours at '70-'90 'F. before use. les, such as formaldehyde yielding mate-- Thissolutibficontains 10% resi solid try-w h rials including paraformaldehyde and hexasand {76% acetic acid based on resin solids, and methyl netetramine,benzaldehyde,furfuraLacetmay -be diluted withcold water as desired. The aldehyde paraldehyde etc m be used v colloidal solution contains about 3.5 mols' of In'general t cationic polymerized aminotfla; acetic acid per mol of methylated trimethylol zine-aldehyde resin colloidal solutions are 'p'remelamine. pared in accordance with the teachings of the The colloidal solutions 'ofca'tio'nic polyme ze Wohnsiedler et al. U. s; Patent No. 2,345,543: arriinotriazinealdehyde condensation '-products We preferusing saturated alip monocar'r" conta sa y be ppl W boxylic'acids havingdisso'ciation constants be-' fabrics in various ways known to thoseskilled in tw en t 4 10 5- n 5 -4 water the art. 'The fabric t0 be treated 35 fi st solubilitiesof at least'about10% for the prepara ro y c eaned'to remove fats a d l etc; tion of the colloidal solutions. Acids'included. The dry fabric is then immersed in theresin dis within this category are hydrocarbon and hyr' persion and passed throughFsuitable rolls'as in a droxyhydrocarbgn a sfollows; padder or mangle tosecure uniform impregn'ation and tolremove excess resin. The fabric, a a 1 however-, maybe'impregnated by other methods 'Acid Constant a such as, for example, by spraying. orwith suit-; 5 able boxes located on the mangle; 'Asour invention is. not limited to any particular, method of impregnating the wool-containing; fabric, other. methods will occur to those skilled in the 'art.--

Since shrinkage controlof-woolen fabrics is most effective and economical within the range of about 5 to 15% by weight of resin, based on the Howeve other. ci s: me d oe ul ri a id.

hydrochloric acid, phosphoric acid, I and the like, mayalso housed. j,

,Just asset forth in the .Wohnsiedier patent referred to above, theexact amount of acid desirable .or necessary forv producing the resin colloids is, variable. In general we prepare our, preferred colloidal polyn'ierizedv resin solutions. using from 0,5 7 mols of the'acid's'. set forth above per-mol of substantially monomeric aminotriazinealdehyde condensation product. More specifically,

the preparation of preferredcolloidal solutions of polymerized methylated methylol'melamineresin,

weight of resin solids based on the dry weight of 1 the wool will be deposited therein.

We claim:

1. A process which comprises impregnating wool with an acidic colloidal aqueous solution of a polymerized, positively charged, aldehyde condensation product of an aminotriazine having at least two amino groups and a hydrogen atom attached to each amino nitrogen atom, said polymerized condensation product having a definite positive electric charge as shown by its migration toward the cathode on electrophoresis of" the solution, said solution containing an amount of acid corresponding to -7 mols of acid per mol of monomeric condensation product, the take-up of the colloidal solution being such as to deposit in the wool from about 2.5%-15,% by weight,'-based' on the dry weightof' the wool, of the polymerizedaminotriazine-aldehyde condensation product and thereafter drying the impregnated. wool whereby the aminotriazine-aldehyde. condensation product deposited in said wool is in a substantially water-insolublecondition.

'2. A process for reducing the felting and shrinking tendencies of wool-containing. fabrics which comprises impregnating a wool containing fabric with an acidic colloidal aqueous solution of a polymerized, positively charged, aldehyde condensation product of an aminotriazinehaving at leasttwo-amino groups and a hydrogen atom attached to each amino nitrogen atom, said polymerized condensation product having adefinite positive electric charge as shown by its migration toward the cathode on electrophoresis of the solution,.said solution containing an amount of acid corresponding to'0.57 mols of acid per mol of monomeric condensation product, the take-up of prises impregnating a wool-containing fabric with an acidic colloidal solution of a polymerized,

positively charged, melamine-formaldehyde condensation product, said polymerized condensation product having a definite positive electric charge 8 ashers by ts..misrai sn.l= wa dibs,catbodaqn1 ec r nhc s s 7i thefso it i eid. o ut ns taming anamount of acidcorresponding to 0,5 7 mols of acid per molof monomeric condensation product, the take-up ofthe colloidal solutionbe: ing such as to deposit the fabric from. about; 15%- by weightbased'on the dry weight 611- the fabric, of the polymerized melamine-forn'ieh de qilde a eli Prod c nd ther afte dr ing he im c naied ahr e eb he ehy e some, sum}, duct. d -1 1 posited in said fabric is in ajsubstantially watere n e e on it on. Y 4. A p ess as isclaim 3 wher e-polyme ed m l e m d hyde on n atien 1 1991 uct is polymerized dimethylol melamine,

5. Aprocess as in claim 3 wherein the polymerz m miner alde y e.cond nsat o .pr d; uct is polymerized trimethylol melamine. I

6. A process as in claim Swherein the polymerized melamine-formaldehyde condensation product is polymerized methylated trimethylol melamine.

1 7. A process for reducing the felting and shrinking tendencies of wool-contaming fabrics which comprises impregnating a Wool-containing fabric with a colloidal aqueous solution of a polymerized, positively charged, formaldehyde condensation product of melamine, said colloidal aqueous solution containing from 0.5-7 mols of a water-soluble, saturated aliphatic monocarboxylic acid selected'from the group consisting of hy- 'drocarbon and hydroxyhydrocarbon acids having dissociation constants between about 1.4X10f and 2.5 10- for each mol of substantially monomeric melamine-formaldehyde condensation product and said polymerized condensation product having a definite positive electrical charge as. shown by its migrationtoward the. cathode upon electrophoresis of the solution, the take-up of the colloidal solution being such as to deposit in the fabric from about 2l5%'-15% by weight, based on the dry weight of the fabric, of the polymerized melamine-formaldehyde condensation product, and thereafter drying the impregnated fabric whereby'the melamine-formaldehyde condensation productis deposited in said fabric in a substantially water-insoluble condition.

8. A process forreducing the felting. and shrinking tendencies of wool-containing fabrics which comprises impregnating a wool-contain:- ing fabric with a colloidal aqueous solution of a polymerized, positively charged, melamine-foremaldehyde condensation; product containing about 3 mols of acetic acid for each mol of sub stantially monomeric melamine-formaldehyde condensation product, said polymerized conden sation product having a definite positive electrical charge as shown by its-migration toward the cathode uponelectrophoresis of the solution, the take-up of the colloidal aqueous solution being such-as to deposit in the fabric from 2.5%-15% by weight, based on the dry weight of the fabric, of the-polymerized melamine-formaldehyde condensation product, and thereafter drying the impregnatedzfabric whereby the mel-- amine-formaldehyde condensation product is deposited'in said fabric ina substantially waterinsoluble condition.

9. A process for reducing the felting and shrinking tendencies of wool-containing fabrics which comprises impregnating a wool-contain ing' fabric with a, colloidal; aqueous solution of a polymerized, pos itivelychar es, melamine 9 formaldehyde condensation product containing about 1.5 mols of formic acid for each mol of substantially monomeric melamine-formaldehyde I condensation product, said polymerized condensation product having a definite positive electrical charge as shown by its migration toward the cathode upon electrophoresis of the solution, the take-up of the colloidal solution being such as to deposit in the fabric from about 2.5 %-15% by weight, based on the dry weight of the fabric, of the polymerized melamine-formaldehyde condensation product, and thereafter drying the impregnated fabric whereby the melamine-formaldehyde condensation product is deposited in said fabric in a substantially water-insoluble condition.

10. A process for reducing the felting and shrinking tendencies of wool-containing fabrics which comprises impregnating a wool-containing fabric with a colloidal aqueous solution of a polymerized, positively charged, melamine-formaldehyde condensation product containing about 2-2.5 mols of glycolic acid for each mol of substantially monomeric melamine-formaldehyde condensation product, said polymerized condensation product having a definite positive electrical charge as shown by its migration toward the cathode upon electrophoresis of the solution, the take-up of the colloidal aqueous solution being such as to deposit in the fabric from 2.5%-15% by weight, based on the dry weight of the fabric, of the polymerized melamine-formaldehyde condensation product, and thereafter drying the impregnated fabric whereby the melamine-formaldehyde condensation product is deposited in said fabric in a substantially water-insoluble condition.

11. A process in accordance with claim 3 wherein the impregnated fabric is dried by heating at a temperature of about 225 F.

LINTON AVERY FLUCK. JOHN EDWARD LYNN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,329,622 Johnstone et a1. Sept. 14, 1943 2,345,543 Wohnsiedler et al. Mar. 28, 1944 2,466,457 Lynn et al. Apr. 5, 1949 2,485,080 Wohnsiedler et al. Oct. 18, 1949 FOREIGN PATENTS Number Country Date 111,833 Australia Aug. 31, 1944 

1. A PROCESS WHICH COMPRISES IMPREGNATING WOOL WITH AN ACIDIC COLLOIDAL AQUEOUS SOLUTION OF A POLYMERIZED, POSITIVELY CHARGED, ALDEHYDE CONDENSATION PRODUCT OF AN AMINOTRIAZINE HAVING AT LEAST TWO AMINO GROUPS AND A HYDROGEN ATOM ATTACHED TO EACH AMINO NITROGEN ATOM, SAID POLYMERIZED CONDENSATION PRODUCT HAVING A DEFINITE POSITIVE ELECTRIC CHARGE AS SHOWN BY ITS MIGRATION TOWARD THE CATHODE ON ELECTROPHORESIS OF THE SOLUTION, SAID SOLUTION CONTAINING AN AMOUNT OF ACID CORRESPONDING TO 0.5-7 MOLS OF ACID PER MOL OF MONOMERIC CONDENSATION PRODUCT, THE TAKE-UP OF THE COLLODIAL SOLUTION BEING SUCH AS TO DEPOSIT IN THE WOOL FROM ABOUT 2.5%-15% BY WEIGHT, BASED ON THE DRY WEIGHT OF THE WOOL, OF THE POLYMERIZED AMINOTRIAZINE-ALDEHYDE CONDENSATION PRODUCT AND THEREAFTER DRYING THE IMPREGNATED WOOL WHEREBY THE AMINOTRIAZINE-ALDEHYDE CONDENSATION PRODUCT DEPOSITED IN SAID WOOL IS IN A SUBSTANTIALLY WATER-INSOLUBLE CONDITION. 